|Publication number||US6423106 B1|
|Application number||US 09/543,280|
|Publication date||Jul 23, 2002|
|Filing date||Apr 5, 2000|
|Priority date||Apr 5, 2000|
|Also published as||WO2001078169A1|
|Publication number||09543280, 543280, US 6423106 B1, US 6423106B1, US-B1-6423106, US6423106 B1, US6423106B1|
|Original Assignee||Johnson Research & Development|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (29), Non-Patent Citations (5), Referenced by (25), Classifications (22), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This invention relates to thin film battery construction, and more particularly to a method of producing the components of a thin film battery.
Lithium-ion batteries have existed for many years. These batteries have high energy and power densities as well as the capability of being cycled thousands of times. The active battery components are a lithium intercalation cathode, e.g. V2O5, LiMn2O4 or LiCoO2, and a lithium metal anode separated by an electrolyte. It has been found the LiCoO2 cathodes have the highest energy and power densities making them attractive as compact rechargeable power sources for application in a varies of electronic devices.
However, thin film lithium batteries cannot be integrated into electronic circuits using the solder reflow method as the temperature required for this process, 250° C.-290° C., is well above the melting point of lithium metal, 180° C. Recently thin film lithium-ion batteries have been developed that are based on inorganic oxynitride and nitride anodes such as silicon-tin oxynitride, tin nitride, or zinc nitride. These batteries can withstand solder reflow temperatures with no adverse effect on battery performance.
However, upon the initial charging of the lithiumion battery approximately one half of the lithium from the LiCoO2 cathode is irreversibly lost to the anode because the oxygen and/or nitrogen in the anode reacts with the lithium to form Li2O and/or Li3N accompanied by the precipitation of silicon and/or tin. Subsequently cycling of the battery occurs through the remaining lithium found in the LixSi and/or LixSi alloys formed in the anode. For example, the reaction on initial charge of a cell with a tin nitride (Sn3N4) anode is:
The anode consists of a lithium-tin alloy (Li22Sn5) in this instance dispersed throughout a solid matrix of Li3N. After the initial charge, the following discharge-charge cycles occurs through the exchange of lithium between the Li22Sn5 in the anode and the LiCoO2 in the cathode:
Accordingly, it is seen that a need remains for a method of producing a thin film battery with minimal capacity loss on the initial charge. It is to the provision of such therefore that the present invention is primarily directed.
In a preferred form of the invention a method of producing a battery cell anode comprises the steps of providing a LixSny target and depositing the LixSny target in an argon-nitrogen atmosphere to form a Sn:Li3N anode, the nitrogen being limited to between 0.5% and 15% of the total volume of the argon-nitrogen atmosphere.
Thin film batteries typically include components which have been built up onto a substrate. The battery includes a cathode, an electrolyte and an anode, wherein each component is provided by a film deposited in a predetermined fashion upon the substrate. The battery may also in include a packaging which provides a barrier against the penetration of air and water vapor.
The substrate underlying the battery may be comprised of glass, alumina or various semiconductor or polymer materials. To enable electrical power to be withdrawn, the battery typically includes two current collector films deposited upon the substrate. The electrolyte may be an amorphous lithium phosphorus oxynitride having the composition LixPOyNz.
To produce the anode in accordance with the present invention, the manufacturing process commences with a sputtering target with a composition of Li3Sn. The target is sputtered in an argon-nitrogen (Ar—N2) gas mixture, wherein the nitrogen gas is limited to within a range of 0.5%-15% of the total volume of gas. The sputtering of the target produces a Sn:Li3N anode layer according to the reaction:
The designation 2Sn:Li3N denotes tin (Sn) dispersed within a matrix of Li3N.
It should be understood that the Sn:Li3N anode eliminates the capacity loss on the initial charging of the battery cell since all of the nitrogen in the anode is already bound in the Li3N and all of the tin (Sn) required for the alloying with the lithium in the cathode is now available for cycling purposes. The composition of the deposited anode film depends on the relative affinities of Sn and Li for nitrogen and on the balancing of the partial pressure of N2 with the sputtering rate.
It is critical to the invention that the atmosphere during the sputtering process limit the amount of available nitrogen to avoid the combining of nitrogen with the tin to form Sn3N4, and to promote the combination of the lithium with the nitrogen. As such, upon initial charging of the battery cell, the lithium within the cathode will not be lost due to its combination with nitrogen within the anode, and as such the lithium is used efficiently in the charging-discharging cycle process.
With the anode of this composition the cycling with can be represented by:
In this equation LiCoO2 represents the pre-charged cathode, the SnLi3N represents the pre-charged anode, the Li22Sn5:5Li3N represents the post-charged anode, and the Li0.5CoO2 represents the post-charged cathode.
It should be understood that the method of the present invention may also be used in connection with other lithium alloying elements, such as nickel, zinc, silicon or tinsilicon. It should also be understood that the sputtering process is equivalent to other methods of chemical and physical vapor deposition, i.e. reactive sputtering or reactive evaporation, such as e-beam evaporation, chemical vapor deposition. As such, the term deposition and depositing as used herein is meant to include all such methods.
While this invention has been described in detail with particular reference to the preferred embodiments thereof, it should be understood that many modifications, additions and deletions, in addition to those expressly recited, may be made thereto without departure from the spirit and scope of invention as set forth in the following claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3237078||Mar 14, 1963||Feb 22, 1966||Mallory & Co Inc P R||Rechargeable batteries and regulated charging means therefor|
|US3393355||Aug 9, 1965||Jul 16, 1968||Mallory & Co Inc P R||Semiconductor charge control through thermal isolation of semiconductor and cell|
|US4303877||May 1, 1979||Dec 1, 1981||Brown, Boveri & Cie Aktiengesellschaft||Circuit for protecting storage cells|
|US4614905||May 18, 1984||Sep 30, 1986||Telefonaktiebolaget Lm Ericsson||Charging regulator|
|US4654281||Mar 24, 1986||Mar 31, 1987||W. R. Grace & Co.||Composite cathodic electrode|
|US4719401||Dec 4, 1985||Jan 12, 1988||Powerplex Technologies, Inc.||Zener diode looping element for protecting a battery cell|
|US5270635||Feb 14, 1992||Dec 14, 1993||Solid State Chargers, Inc.||Universal battery charger|
|US5291116||Sep 23, 1992||Mar 1, 1994||Batonex, Inc.||Apparatus for charging alkaline zinc-manganese dioxide cells|
|US5314765 *||Oct 14, 1993||May 24, 1994||Martin Marietta Energy Systems, Inc.||Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method|
|US5336573||Jul 20, 1993||Aug 9, 1994||W. R. Grace & Co.-Conn.||Battery separator|
|US5338625||Jul 29, 1992||Aug 16, 1994||Martin Marietta Energy Systems, Inc.||Thin film battery and method for making same|
|US5362581||Apr 1, 1993||Nov 8, 1994||W. R. Grace & Co.-Conn.||Battery separator|
|US5387857||Feb 7, 1992||Feb 7, 1995||Honda Giken Kogyo Kabushiki Kaisha||Battery charging apparauts|
|US5399246 *||Aug 26, 1993||Mar 21, 1995||Ceramatec, Inc.||Inert gas purification|
|US5411592||Jun 6, 1994||May 2, 1995||Ovonic Battery Company, Inc.||Apparatus for deposition of thin-film, solid state batteries|
|US5445906||Aug 3, 1994||Aug 29, 1995||Martin Marietta Energy Systems, Inc.||Method and system for constructing a rechargeable battery and battery structures formed with the method|
|US5455126||May 25, 1994||Oct 3, 1995||Martin Marietta Energy Systems, Inc.||Electra-optical device including a nitrogen containing electrolyte|
|US5512147||May 25, 1994||Apr 30, 1996||Martin Marietta Energy Systems, Inc.||Method of making an electrolyte for an electrochemical cell|
|US5561004||Feb 25, 1994||Oct 1, 1996||Bates; John B.||Packaging material for thin film lithium batteries|
|US5567210||Jul 12, 1994||Oct 22, 1996||Martin Marietta Energy Systems, Inc.||Method for making an electrochemical cell|
|US5569520||Jun 7, 1995||Oct 29, 1996||Martin Marietta Energy Systems, Inc.||Rechargeable lithium battery for use in applications requiring a low to high power output|
|US5597660||May 25, 1994||Jan 28, 1997||Martin Marietta Energy Systems, Inc.||Electrolyte for an electrochemical cell|
|US5612152||Apr 17, 1996||Mar 18, 1997||Martin Marietta Energy Systems, Inc.||Rechargeable lithium battery for use in applications requiring a low to high power output|
|US5654084||Jul 22, 1994||Aug 5, 1997||Martin Marietta Energy Systems, Inc.||Protective coatings for sensitive materials|
|US5778515||Apr 11, 1997||Jul 14, 1998||Valence Technology, Inc.||Methods of fabricating electrochemical cells|
|US5783928||Apr 2, 1993||Jul 21, 1998||Jeol Ltd.||Storage capacitor power supply|
|US5811205||Dec 27, 1995||Sep 22, 1998||Saft||Bifunctional electrode for an electrochemical cell or a supercapacitor and a method of producing it|
|US5821733||Dec 16, 1996||Oct 13, 1998||Packard Bell Nec||Multiple cell and serially connected rechargeable batteries and charging system|
|US5919587 *||May 21, 1997||Jul 6, 1999||Moltech Corporation||Composite cathodes, electrochemical cells comprising novel composite cathodes, and processes for fabricating same|
|1||Journal of Materials Science, Unique porous LiCoO2 thin layers prepared by electrostatic spray deposition. C.H. Chen et al., 1996.|
|2||Journal of Power Sources, P. Fragnaud, R. Nagarajan, D.M. Schleich, D. Vujic, Thin-film cathodes for secondary lithium batteries, 1995.|
|3||Journal of Power Sources, Thin film solid electrolytes and electrodes for rechargeable lithium-ion batteries, J. Schoonman, E.M. Kelder, 1997.|
|4||Materials Research Society, The Preparation and Characterization of Lithium Cobalt Oxide Thin Films by LPCVD, 1996.|
|5||Solid State Ionics, Fabrication of LiCoO2 thin film cathodes for rechargeable lithium battery by electrostatic spray pyrolysis, C.H. Chen et al., 1995.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US6653020 *||Apr 12, 2001||Nov 25, 2003||Rutgers University Foundation||Metal nitride electrode materials for high capacity rechargeable lithium battery cells|
|US7959769||Jun 14, 2011||Infinite Power Solutions, Inc.||Deposition of LiCoO2|
|US7993773||Aug 21, 2009||Aug 9, 2011||Infinite Power Solutions, Inc.||Electrochemical apparatus with barrier layer protected substrate|
|US8021778||Aug 23, 2005||Sep 20, 2011||Infinite Power Solutions, Inc.||Electrochemical apparatus with barrier layer protected substrate|
|US8062708||Sep 26, 2007||Nov 22, 2011||Infinite Power Solutions, Inc.||Masking of and material constraint for depositing battery layers on flexible substrates|
|US8197781||Jun 12, 2012||Infinite Power Solutions, Inc.||Sputtering target of Li3PO4 and method for producing same|
|US8236443||Mar 16, 2007||Aug 7, 2012||Infinite Power Solutions, Inc.||Metal film encapsulation|
|US8260203||Sep 4, 2012||Infinite Power Solutions, Inc.||Energy device with integral conductive surface for data communication via electromagnetic energy and method thereof|
|US8268488||Jan 23, 2009||Sep 18, 2012||Infinite Power Solutions, Inc.||Thin film electrolyte for thin film batteries|
|US8350519||Jan 8, 2013||Infinite Power Solutions, Inc||Passive over/under voltage control and protection for energy storage devices associated with energy harvesting|
|US8394522||Apr 29, 2008||Mar 12, 2013||Infinite Power Solutions, Inc.||Robust metal film encapsulation|
|US8404376||Mar 26, 2013||Infinite Power Solutions, Inc.||Metal film encapsulation|
|US8431264||Jul 25, 2008||Apr 30, 2013||Infinite Power Solutions, Inc.||Hybrid thin-film battery|
|US8445130||Nov 17, 2006||May 21, 2013||Infinite Power Solutions, Inc.||Hybrid thin-film battery|
|US8508193||Oct 7, 2009||Aug 13, 2013||Infinite Power Solutions, Inc.||Environmentally-powered wireless sensor module|
|US8518581||Jan 9, 2009||Aug 27, 2013||Inifinite Power Solutions, Inc.||Thin film encapsulation for thin film batteries and other devices|
|US8535396||Aug 21, 2009||Sep 17, 2013||Infinite Power Solutions, Inc.||Electrochemical apparatus with barrier layer protected substrate|
|US8599572||Sep 1, 2010||Dec 3, 2013||Infinite Power Solutions, Inc.||Printed circuit board with integrated thin film battery|
|US8636876||Dec 7, 2005||Jan 28, 2014||R. Ernest Demaray||Deposition of LiCoO2|
|US8728285||May 20, 2004||May 20, 2014||Demaray, Llc||Transparent conductive oxides|
|US8906523||Aug 11, 2009||Dec 9, 2014||Infinite Power Solutions, Inc.||Energy device with integral collector surface for electromagnetic energy harvesting and method thereof|
|US9334557||Dec 19, 2008||May 10, 2016||Sapurast Research Llc||Method for sputter targets for electrolyte films|
|US20100090655 *||Oct 7, 2009||Apr 15, 2010||Keating Joseph A||Environmentally-Powered Wireless Sensor Module|
|DE102014225350A1 *||Dec 10, 2014||Jun 16, 2016||Bayerische Motoren Werke Aktiengesellschaft||Elektroden-Aktivmaterial für einen Lithium-haltigen Energiespeicher|
|WO2008036731A2||Sep 19, 2007||Mar 27, 2008||Oak Ridge Micro-Energy||Thin film battery hermetic package|
|U.S. Classification||29/623.1, 429/218.1, 29/623.5, 429/231.95|
|International Classification||H01M4/13, H01M6/40|
|Cooperative Classification||Y02P70/54, Y10T29/49108, Y10T29/49115, Y02E60/122, H01M4/0404, H01M6/40, H01M4/13, H01M4/0426, H01M4/04, H01M4/0495|
|European Classification||H01M4/13, H01M4/04B18B2, H01M4/04, H01M6/40, H01M4/04N4, H01M4/04B2|
|Apr 5, 2000||AS||Assignment|
Owner name: JOHNSON RESEARCH & DEVELOPMENT COMPANY, INC., GEOR
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BATES, JOHN;REEL/FRAME:010729/0040
Effective date: 20000329
|Dec 11, 2000||AS||Assignment|
Owner name: EXCELLATRON SOLID STATE, LLC, GEORGIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:JOHNSON RESEARCH AND DEVELOPMENT CO., INC.;REEL/FRAME:011370/0304
Effective date: 20001017
|Feb 8, 2006||REMI||Maintenance fee reminder mailed|
|Jul 24, 2006||LAPS||Lapse for failure to pay maintenance fees|
|Sep 19, 2006||FP||Expired due to failure to pay maintenance fee|
Effective date: 20060723